Liquid deodorant killing microorganism and method of microorganism-killing deodorization

ABSTRACT

The object of the present invention is to provide a microbicidal deodorant in a tractable liquid form that has excellent long-term storage stability. 
     The microbicidal deodorant of the present invention comprises: at least one substance selected from the group consisting of halogenated dialkyl hydantoins represented by the general formula (1) and halogenated succinimides represented by general formula (2); and at least one substance selected from the group consisting of tetrahydrothiophene 1,1-dioxide, 3-methyltetrahydrothiophene 1,1-dioxide, and 2,5-dihydrothiophene 1,1-dioxide.

TECHNICAL FIELD

The present invention relates to a microbicidal liquid deodorant, adeodorizing method for killing microbes using the same, and a method forstabilizing a microbicidal liquid deodorant. More specifically, thepresent invention relates to a novel microbicidal liquid agentcontaining a halogenated dialkyl hydantoin and a halogenated succinimidewhich are stabilized by thiophene derivatives such astetrahydrothiophene-1,1-dioxide and a method for killing microbes usingthe above, a liquid deodorant and a deodorizing method using the same,and a method for stabilizing these agents.

BACKGROUND ART

In recent years, there have many instances of trouble occurring due tothe presence of slime in various types of service water traceable tomicrobial contamination, and adverse effects have been caused in variousfields. Here, the term “slime” means a sticky aggregated or muddysubstance which comprises as major components high molecularpolysaccharides secreted mainly by microbes, and various types ofsubstance suspended in the water which become incorporated therein. Forexample, when slime occurs in heat exchangers or pipes of a coolingwater system at a chemical factory or the like, cooling efficiency isdecreased and sometimes pipes are clogged. Further, when slime forms onthe wall surfaces of pipes used in the paper manufacturing process at apaper factory, the slime is flaked off and mixed in white water (backwater). Then, spots or coloring are formed on the paper product anddeteriorate its quality. This partially decreases paper strength andthus causes paper breakages, forcing the interruption of continuousoperations. Therefore, the control of the causative microbes is animportant issue.

Further, active sludge at sewage treatment plants, unpleasant odors fromwastes or residues, and foul odors from raw garbage at waste treatmentplants cause not only on-site working environments to be poor, but alsodeteriorate the environments of surrounding areas by diffusing suchodors to these areas. Thus, prompt odor elimination or deodorization bypreventing the occurrence of or by the decomposition of causative agentsis essential. However, in the case of existing deodorants, thedecomposition or volatilization of their chemical components havingdeodorant effects results in deterioration of their deodorant effects,and the problem thus exists that the sustainability of their effects islow.

Conventionally, chlorine gas, sodium hypochlorite or potassiumhypochlorite solution, or chlorinated isocyanuric acid in tablet orpowder form has been used in order to prevent trouble caused by suchmicrobes. However, chlorine gas has disadvantages in that it involvesvery high risk in the case of leakage, and it is difficult to handle.Further, hypochlorous agents are also disadvantageous in that they donot act effectively on microbes since they do not have permeability intoslime. These agents have further disadvantages such as deactivation byorganic matters in water, and thus sufficient efficacy cannot beexpected.

On the other hand, it is known that halogenated dialkyl hydantoins orhalogenated succinimides have microbicidal activities (Zn. Mikrobiol.,Epidemiol. Immunobiol. vol.14, No.9, p14-18, 1967, JP Patent Publication(Examined Application) No. 46-27270). However, these compounds arecommercially distributed in a solid form such as tablet, powder, orgranule, and they are used in the solid form in the field. Therefore,when using these compounds, problems arise in handling safety, that is,the risk of effects on humans such as skin disorders and mucosalinflammation caused by dusting during operation. Further, workabilityproblems are presented, such as the inability to transfer thesecompounds by pump.

Further, from a microbicidal efficacy aspect, these compounds havesluggish solubility and permeability into target systems. Thus, in orderto obtain a sufficient effect in a short period, these compounds must beadded in a large amount. In particular, when these compounds are usedfor water systems with low recirculation rates, for example, coolingwater for certain industrial uses or water for paper manufacturingprocesses, water in the systems is discharged out of the systems beforethe inputted compounds are completely dissolved. In contrast, when thesecompounds are used for water systems with high recirculation rates, forexample, cooling water for air-conditioning, the sluggish rate ofdissolution of the inputted compounds increases the probability of thegrowth of resistant microbes in the system. Also, due to the sluggishrate of dissolution and sluggish permeability of these compounds, promptdeodorizing effects after their input cannot be obtained. Therefore, inthe case of using these compounds as deodorants, the addition of largeamounts thereof is required, resulting in cost increase.

Most solid compounds having microbicidal activity are used as liquidagent by dissolving them into, in general, glycols, glycol ethers,aprotic polar solvents or water, or mixture solvents of these withwater. This allows easy handling of microbicidal solid compounds.Liquidizing microbicidal solid compounds in this manner provides thesecompounds with excellent workability at the time of use, and at the sametime, also provides them with other advantages such as quick dissolutionand permeation of active ingredients into target systems to be treatedfor microbes or deodorization. Namely, in comparison with the case wheresolid compounds are inputted into the target systems as solid agents,adding smaller amounts of these compounds within a shorter periodenables killing of microbes and deodorization in the target systems.Therefore, liquidizing microbicidal solid compounds is an extremelyeffective means for cost reduction.

However, when halogenated dialkyl hydantoins and halogenatedsuccinimides are prepared as liquid agents with generally used organicsolvents, a large volume of irritant corrosive gas is immediatelygenerated. Further, in this case, microbicidal active ingredients aredeactivated within a very short period, and thus the compounds can nolonger be used as microbicidal and deodorizing agents. In other words,liquid agents containing halogenated dialkyl hydantoins and halogenatedsuccinimides have disadvantages such as corrosive gas generation andpoor stability. Furthermore, with regard to liquid compositionscontaining derivatives of halogenated dialkyl hydantoins, a method usingwater and cyclic amide compounds including ε-caprolactam and succinimidehas been already suggested (JP Patent Publication (Examined Application)No. 56-37961). Although these liquid compositions are better in terms ofstability in comparison with liquid compositions prepared using commonorganic solvents, they do not have sufficient stability as aformulation.

Under these circumstances, there is a need for halogenated dialkylhydantoin compositions and halogenated succinimide compositions whichare liquid for tractability and have excellent stability, i.e. stable inlong-term storage. However, a formulated liquid agent suitable forpractical use has not been found before.

DISCLOSURE OF INVENTION

In order to solve the above problems, it is an object of the presentinvention to provide a liquid microbicidal deodorant which comprises ahalogenated dialkyl hydantoin and/or a halogenated succinimide as anactive ingredient and has excellent workability, safety, stability, andsolubility, and a method for killing microbes and deodorizing.

The present inventors have carried out intensive research on the aboveobject. As a result, they have succeeded in formulating a liquid agentin which an effective active ingredient is maintained over a long periodbut which does not generate any irritant and corrosive gas by using atleast one substance selected from the group consisting oftetrahydrothiophene 1,1-dioxide, 3-methyltetrahydrothiophene1,1-dioxide, and 2,5-dihydrothiophene 1,1-dioxide as a primary solvent.Thus, according to the present invention, there is provided a liquidmicrobicide and a liquid deodorant which comprise a halogenated dialkylhydantoin and/or halogenated succinimide in a stable state, and a methodfor killing microbes and a method for deodorizing using these. Namely,the present invention includes the following:

-   (1) A liquid microbicide comprising: at least one substance selected    from the group consisting of halogenated dialkyl hydantoins    represented by the following general formula (1):-    wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent    low alkyl groups, and-   halogenated succinimides represented by the following general    formula (2):-    wherein Y represents a halogen atom; and-   at least one substance selected from the group consisting of    tetrahydrothiophene 1,1-dioxide, 3-methyltetrahydrothiophene    1,1-dioxide, and 2,5-dihydrothiophene 1,1-dioxide.-   (2) The liquid microbicide described in (1) above, wherein the    halogenated dialkyl hydantoin is 1,3-dibromo-5,5-dimethylhydantoin,    1-bromo-3-chloro-5,5-dimethylhydantoin,    3-bromo-1-chloro-5,5-dimethylhydantoin,    bromochloro-5,5-dimethylhydantoin,    1,3-dichloro-5,5-dimethylhydantoin, or    1,3-dichloro-5-ethyl-5-methylhydantoin.-   (3) The liquid microbicide described in (1) above, wherein the    halogenated succinimide is N-chlorosuccinimide or    N-bromosuccinimide.-   (4) The liquid microbicide described in (1) above, comprising a    halogenated dialkyl hydantoin and tetrahydrothiophene 1,1-dioxide.-   (5) The liquid microbicide described in any one of (1) to (4) above,    further comprising at least one substance selected from the group    consisting of hydantoin, 5,5-dimethylhydantoin, succinimide, and    phthalimide.-   (6) The liquid microbicide described in any one of (1) to (5) above,    further comprising a known microbicide component.-   (7) A method for killing microbes, comprising the step of treating a    target system or a target object for microbicidal treatment with the    liquid microbicide described in any one of (1) to (6) above.-   (8) A liquid deodorant comprising at least one substance selected    from the group consisting of halogenated dialkyl hydantoins    represented by the above general formula (1) and halogenated    succinimides represented by the above general formula (2), and at    least one substance selected from the group consisting of    tetrahydrothiophene 1,1-dioxide, 3-methyltetrahydrothiophene    1,1-dioxide, and 2,5-dihydrothiophene 1,1-dioxide.-   (9) The liquid deodorant described in (8) above, wherein the    halogenated dialkyl hydantoin is 1,3-dibromo-5,5-dimethylhydantoin,    1-bromo-3-chloro-5,5-dimethylhydantoin,    3-bromo-1-chloro-5,5-dimethylhydantoin,    bromochloro-5,5-dimethylhydantoin,    1,3-dichloro-5,5-dimethylhydantoin, or    1,3-dichloro-5-ethyl-5-methylhydantoin.-   (10) The liquid deodorant described in (8) above, wherein the    halogenated succinimide is N-chlorosuccinimide or    N-bromosuccinimide.-   (11) The liquid deodorant described in (8) above, comprising a    halogenated dialkyl hydantoin and tetrahydrothiophene 1,1-dioxide.-   (12) The liquid deodorant described in any one of (8) to (11) above,    further comprising at least one substance selected from the group    consisting of hydantoin, 5,5-dimethylhydantoin, succinimide, and    phthalimide.-   (13) The liquid deodorant described in any one of (8) to (12) above,    further comprising a known microbicide component.-   (14) A deodorizing method comprising the step of treating a target    object or a target system for deodorization with the liquid    deodorant described in any one of (8) to (13) above.-   (15) A method for stabilizing a halogenated dialkyl hydantoin and/or    halogenated succinimide, comprising the step of: dissolving at least    one substance selected from the group consisting of halogenated    dialkyl hydantoins represented by the above general formula (1) and    halogenated succinimides represented by the above general formula    (2), in at least one substance selected from the group consisting of    tetrahydrothiophene 1,1-dioxide, 3-methyltetrahydrothiophene    1,1-dioxide, and 2,5-dihydrothiophene 1,1-dioxide.-   (16) The method for stabilizing a halogenated dialkyl hydantoin    and/or halogenated succinimide described in (15) above, wherein at    least one substance selected from the group consisting of hydantoin,    5,5-dimethylhydantoin, succinimide, and phthalimide is dissolved.

The halogenated dialkyl hydantoin to be used for the liquid microbicideand liquid deodorant (hereinafter referred to as microbicidal liquiddeodorant) of the present invention is represented by the above generalformula (1). In the general formula (1), examples of halogen representedby X¹ and X² include bromide and chlorine. Here, X¹ and X² may be thesame or different. Further, examples of lower alkyl groups representedby R¹ and R² include alkyl groups having a carbon number from 1 to 3,such as methyl groups, ethyl groups, and propyl groups, and preferablyalkyl groups having a carbon number from 1 to 2. Here, R¹ and R² may bethe same or different. These halogenated dialkyl hydantoins can beproduced by first obtaining dialkyl hydantoin from a dialkyl ketone, acyanide, or a carbonate, and halogenating dialkyl hydantoin.

Specific compounds of the halogenated dialkyl hydantoin are exemplifiedas follows.

-   Compound A1: 1,3-dibromo-5,5-dimethylhydantoin-   Compound A2: 1-bromo-3-chloro-5,5-dimethylhydantoin-   Compound A3: 3-bromo-1-chloro-5,5-dimethylhydantoin-   Compound A4: bromochloro-5,5-dimethylhydantoin-   Compound A5: 1,3-dichloro-5,5-dimethylhydantoin-   Compound A6: 1,3,-dichloro-5-ethyl-5-methylhydantoin

These halogenated dialkyl hydantoins may be used either alone or incombination of two or more. Among these compounds, the selection for useis preferably carried out from the group consisting of compounds A1 toA4.

Halogenated dialkyl hydantoins are commercially available, and these maybe used. Examples of commercially available halogenated dialkylhydantoin include HALOCOM DBH (High Polymer Labs, the above-describedCompound A1), AQUABROM (Great Lakes Chemical Corporation, theabove-described Compound A2), and DANTOBROM RW (Lonza, a mixture of theabove-described Compounds A4, A5, and A6).

Further, the halogenated succinimide to be used for the microbicidalliquid deodorant is represented by the above general formula (2). In thegeneral formula (2), examples of halogen represented by Y includebromide and chlorine. These halogenated succinimides are produced byhalogenating succinimide using a halogenating agent such as metalhypochlorite or hypochlorite.

Specific compounds of halogenated succinimides are exemplified asfollows.

-   Compound B1: N-bromosuccinimide-   Compound B2: N-chlorosuccinimide

The halogenated succinimides may be used either alone or in combinationof two or more. Further, the halogenated dialkyl hydantoin andhalogenated succinimide may be used in combination for the microbicidalliquid deodorant of the present invention.

Thiophene derivatives to be used as a primary solvent for themicrobicidal liquid deodorant of the present invention are exemplifiedas follows.

-   Compound C1: tetrahydrothiophene 1,1-dioxide-   Compound C2: 3-methyltetrahydrothiophene 1,1-dioxide-   Compound C3: 2,5-dihydrothiophene 1,1-dioxide

These thiophene derivatives may be used either alone or in combinationof two or more. Namely, at least one compound selected from the groupconsisting of Compounds C1 to C3 is used as a primary solvent for themicrobicidal liquid deodorant of the present invention.

The microbicidal liquid deodorant of the present invention is preparedby mixing and stirring at least one substance selected from the groupconsisting of halogenated dialkyl hydantoins (general formula (1)) andhalogenated succinimides (general formula (2)), and at least one of theabove thiophene derivatives. In some cases, the mixing and stirring arepreferably conducted while heating at 40 to 50° C. for 10 minutes toapproximately 1 hour.

Further, an adjuvant or the like is preferably added to the microbicidalliquid deodorant. Examples of the adjuvant include at least onesubstance selected from the group consisting of hydantoin,5,5-dimethylhydantoin, succinimide, and phthalimide. The solubility ofhalogenated dialkyl hydantoin and/or halogenated succinimide can befurther enhanced by inclusion of the adjuvant in the microbicidal liquiddeodorant. As long as the adjuvant is a compound selected from the groupmentioned above, these may be used either alone or in combination of twoor more.

The above-mentioned primary solvent is preferably mixed in an amount of100 or more parts by mass, more preferably 200 to 900 parts by mass,based on 100 parts by mass of halogenated dialkyl hydantoin and/orhalogenated succinimide. Employing the above range of the mixing amountof the primary solvent can enhance the stability of the microbicidalliquid deodorant.

In addition, the adjuvant is preferably mixed in an amount of 1 to 50parts by weight, more preferably 5 to 20 parts by weight, based on 100parts by mass of halogenated dialkyl hydantoin and/or halogenatedsuccinimide.

Furthermore, the microbicidal liquid deodorant of the present inventionmay be mixed with a generally used inexpensive organic solvent and/orwater at the time of formulation or practical use.

Examples of usable organic solvents include: glycols such as ethyleneglycol, diethylene glycol, dipropylene glycol, and polyethylene glycol;glycol ethers such as ethyl cellosolve, methyl carbitol, and dipropyleneglycol monomethyl ether; esters such as propylene carbonate,4-butyrolactone, dimethyl glutarate, dimethyl adipate, dimethylsuccinate, and dimethyl maleate; amides such as N-methylacetamide,acetamide, 2-pyrrolidinone, and ε-caprolactam; and alcohols such asisopropyl alcohol and octanol. Among these, it is particularlypreferable to use propylene carbonate, 4-butyrolactone, 2-pyrrolidinone,and N-methylacetamide. These organic solvents may be used either aloneor in combination of two or more.

The microbicidal liquid deodorant of the present invention may bediluted with these organic solvents and/or water at an arbitrarydilution ratio. The mixing ratio of organic solvent and/or water ispreferably 1 to 99% by mass, more preferably 10 to 90% by mass, and mostpreferably 30 to 70% by mass.

The microbicidal liquid deodorant of the present invention may be usedfor the purpose of killing microbes, deodorizing, or both of these. Thetargets for application of the microbicidal liquid deodorant, that issystems or objects to be treated for killing microbes and deodorizing,are not particularly limited, and various applications are possible. Themicrobicidal liquid deodorant of the present invention can exhibitmicrobicidal and/or deodorant effects more quickly than the conventionalsolid type. As target objects for application of the microbicidal liquiddeodorant, paper manufacturing processes, cooling or washing water forindustrial use, cooling water for air-conditioning, industrial water,pools, baths, activated sludge wastes or residues, and raw garbage areexemplified. When the microbicidal liquid deodorant is used for papermanufacturing processes, cooling or washing water for industrial use,cooling water for air-conditioning, industrial water, pools, baths,etc., disinfection and bacteriostasis can be effectively accomplishedand slime formation can also be inhibited. Further, when themicrobicidal liquid deodorant is used for activated sludge wastes orresidues, raw garbage, etc., deodorization can effectively beaccomplished.

A proper input amount of the microbicidal liquid deodorant differs andis appropriately determined depending on the pH of the target object orsystem, the contents of organic or inorganic matters, the odorintensity, or the like. Generally, the input amount is determined suchthat halogenated dialkyl hydantoin and/or halogenated succinimide arepresent in a concentration of 0.1 to 1000 ppm, preferably 5 to 100 ppm.Inputting an amount of the microbicidal liquid deodorant within theabove range produces sufficient microbicidal and/or deodorant effects aswell as concurrent economical advantages.

Combining the microbicidal liquid deodorant of the present inventionwith known microbicide components enables the enlargement of theantibacterial spectrum, and the obtainment of additional or synergisticeffects of the antibacterial ability. Examples of known microbicidecomponents include bromonitro compounds such as2,2-dibromo-2-nitroethanol, 2,2-dibromo-2-nitroethyl=formate,2,2-dibromo-2-nitroethyl=acetate, 2,2-dibromo-2-nitroethyl=propanoate,2-bromo-2-nitropropane-1,3-diol, 2-bromo-2-nitropropan-1,3-diyl=diorama,and 2-bromo-2-nitropropane-1,3-diyl=diacetate (hereinafter referred toas “BNDA”), methylenbisthiocyanate,3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide,5-chloro-2,4,6-trifluoroisophthalonitrile,1-bromomethyl-2-bromo-1,2-ethanedinitrile, di-n-decyl dimethyl ammoniumchloride, and benzalkonium chloride. Among these,2,2-dibromo-2-nitroethanol or 2-bromo-2-nitropropane-1,3-diyl=acetate ispreferably mixed.

Target microbes to be treated with the microbicidal liquid deodorant ofthe present invention may include bacterium, eumycetes such as yeastsand filamentous fungus, and algae. Examples of bacterium include: gramnegative bacterium such as Escherichia genus, Pseudomonas genus, Vibriogenus, Enterobacter genus, Serratia genus, Legionella genus, andSalmonella genus; and gram positive bacterium such as Staphylococcusgenus, Bacillus genus, Streptococcus genus, and Lactobacillus genus.Examples of yeasts include Saccharomyces genus, Candida genus,Geotrichum genus, Hansenula genus, Rhodotrula genus, Kluyveromycesgenus, and Pichia genus. Examples of filamentous fungus includeAspergillus genus, Penicillium genus, Trichoderma genus, Mucor genus,Rhizopus genus, Fusarium genus, Cladosporium genus, and Alternariagenus. Examples of algae include Chlorella genus, Oscillatoria genus,Anabaena genus, Senedesmus genus, and Clostetium genus.

INDUSTRIAL APPLICABILITY

The microbicidal liquid deodorant of the present invention can maintainhalogenated dialkyl hydantoin and/or halogenated succinimide, which havebeen difficult to liquidize in a stable condition, in a stable conditionover a long-term. Therefore, according to the present invention, thereis provided a microbicidal liquid deodorant which can be preservedwithout change of properties as a liquid agent for a long term. Further,since the microbicidal liquid deodorant of the present invention is aliquid agent, it can exhibit prompt microbicidal and/or deodoranteffects, which are not observed in the case of solid agents. Thus, thepresent invention provides a microbicidal liquid deodorant which hasexcellent safety and workability and is free from dusting, a drawback ofthe solid agents.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention will hereinafter be described in detail withreference to Examples, Comparative Examples and Test Examples, but thetechnical scope of the present invention is not limited thereto.Examples were obtained by mixing with each component and stirring withheat at 45° C. for 15 minutes. The mixture of compounds A4, A5, and A6used in the tests was prepared by mixing the compounds at a ratio of 60,30, and 10 parts by weight, respectively.

TABLE 1 Composition Formulation (% by mass) Example 1 Compound A1 12.0Compound C1 88.0 Example 2 Compound A2 30.0 Compound C1 66.05,5-dimethylhydantoin 4.0 Example 3 Mixture of Compound A4, A5, and 18.0A6 (6:3:1) Compound C1 50.0 4-butyrolactone 32.0 Example 4 Compound B115.0 Compound C1 85.0 Example 5 Compound B2 10.0 Compound C1 40.0propylene carbonate 50.0 Example 6 Compound A1 12.0 Compound C2 88.0Example 7 Compound A2 12.0 Compound C1 88.0 Example 8 Compound A1 20.0Compound C1 77.5 hydatoin 2.5 Example 9 Compound A2 42.0 Compound C153.0 hydatoin 5.0 Example 10 Compound A2 25.0 Compound C1 46.5 CompoundC2 25.0 succinimide 3.5 Example 11 Mixture of Compound A4, A5, and 15.0A6 (6:3:1) Compound C1 80.0 Compound C3 5.0 Example 12 Compound B1 20.0Compound C2 78.0 phtahlimide 2.0 Example 13 Compound A1 15.0 Compound C170.0 BNDA 15.0 Comparative Compound A1 12.0 Example 1N,N-dimethylacetamide 88.0 Comparative Compound A2 20.0 Example 2ε-caprolactam 45.0 water 35.0 Comparative Compound A2 10.0 Example 3N-methyl-2-pyrrolidinone 90.0 Comparative Compound B1 10.0 Example 44-butyrolactone 90.0 Comparative Compound B2 10.0 Example 54-butyrolactone 90.0

TEST EXAMPLE 1 Stability Test

Twenty-ml graduated test tubes were filled respectively with eachcompound having the formulation shown in Table 1, and each of the testtubes was sealed so as to leave no bubbles with a silicone stopperhaving a U-shaped glass tube, one side of which was attached topenetrate the silicone stopper for discharging generated gas. Each wholedevice was placed gently inside a glass beaker and the opening of thebeaker was covered with aluminum foil. The beaker was allowed to standin an incubator at 40° C. for a predetermined number of days. The volumeof gas generated with the lapse of time was measured by reading thegraduation, and corrosion of the aluminum foil caused by the generatedgas was observed. The results are shown in Tables 2 and 3. Tables 2 and3 indicate the respective results obtained by conducting the tests overtwo separate occasions under the above conditions.

TABLE 2 Lapse of days 3 days 7 days 14 days 28 days Example 1 Volume of0 0 0 0 generated gas (ml) Presence of none none none none corrosionExample 2 Volume of 0 0 0 0.0 generated gas (ml) Presence of none nonenone none corrosion Example 3 Volume of 0 0 0 0 generated gas (ml)Presence of none none none none corrosion Example 4 Volume of 0 0 0 0.2generated gas (ml) Presence of none none none none corrosion Example 5Volume of 0 0 0 0 generated gas (ml) Presence of none none none nonecorrosion Comparative Volume of 0.4 2.0 4.5 7.0 Example 1 generated gas(ml) Presence of none present present present corrosion ComparativeVolume of 0 0.3 1.1 2.6 Example 2 generated gas (ml) Presence of nonenone present present corrosion Comparative Volume of 0.2 1.8 5.0 6.5Example 3 generated gas (ml) Presence of present present present presentcorrosion Comparative Volume of 0.2 1.7 3.0 4.5 Example 4 generated gas(ml) Presence of present present present present corrosion

TABLE 3 Lapse of days 3 days 7 days 14 days 28 days Example 8 Volume of0 0 0 0 generated gas (ml) Presence of none none none none corrosionExample 9 Volume of 0 0 0 0 generated gas (ml) Presence of none nonenone none corrosion Example 10 Volume of 0 0 0 0 generated gas (ml)Presence of none none none none corrosion Example 11 Volume of 0 0 0 0.2generated gas (ml) Presence of none none none none corrosion Example 12Volume of 0 0 0 0 generated gas (ml) Presence of none none none nonecorrosion Comparative Volume of 0.6 2.5 4.0 6.0 Example 1 generated gas(ml) Presence of none present present present corrosion ComparativeVolume of 0 0.5 1.6 3.0 Example 2 generated gas (ml) Presence of nonepresent present present corrosion Comparative Volume of 0.5 1.8 4.0 6.0Example 3 generated gas (ml) Presence of present present present presentcorrosion Comparative Volume of 0.2 0.4 2.5 4.0 Example 5 generated gas(ml) Presence of present present present present corrosion

The results of Tables 2 and 3 show that the Examples generated anextremely smaller volume of gas compared with the Comparative Examplesand did not cause corrosiveness. Thus, it was found that the Examplesare safe and stable microbicidal liquid deodorants.

TEST EXAMPLE 2 Confirmation Test for Stability of Microbicidal Effects

Each compound having the formulation of Table 1 was poured into a glassbottle, and each glass bottle was sealed hermetically, and allowed tostand in an incubator at 50° C. for 4 weeks. The compounds of thesebottles were compared with the just-prepared unheated liquid agents interms of microbicidal activity. Escherichia genus microbes, which weresubjected to cell washing, were added to phosphate/citrate buffersolution (pH 8) to a concentration of approximately 10⁶ CFU/ml, and eachliquid agent was then added thereto so as to have a prescribedconcentration (indicated based on active ingredient) and the mixture wasshaken for 1 hour in an L shape tube. Thereafter, each mixture wasdiluted with sterilized water, inoculated onto a nutrient plate agarmedium, and cultured in an incubator for 3 days at 30° C. Then, viablecells therein were counted. The results are shown in Tables 4 and 5 inthe unit of CFU/ml. Tables 4 and 5 indicate the respective resultsobtained by conducting the tests over two separate occasions under theabove conditions.

TABLE 4 No heating Conc. Heating (Immediately after (ppm) (50° C., 4weeks) preparation) Example 1 0.96 <10² <10² 0.72 <10² <10² 0.48 2.0 ×10² <10² 0.24 5.1 × 10⁶ 7.1 × 10⁵ Example 2 1.8 <10² <10² 1.2 <10² <10²0.6 <10² <10² 0.3 4.8 × 10⁵ 6.9 × 10⁵ Example 4 1.2 <10² <10² 0.9 <10²<10² 0.6 <10² <10² 0.3 6.0 × 10⁴ 4.0 × 10⁴ Example 5 0.8 <10² <10² 0.6<10² <10² 0.4 1.0 × 10³ 8.0 × 10² 0.2 1.1 × 10⁵ 4.0 × 10⁵ Comparative3.84 7.0 × 10⁶ <10² Example 1 1.92 4.9 × 10⁶ <10² 0.96 5.4 × 10⁶ 2.0 ×10² 0.48 5.5 × 10⁶ 7.0 × 10³ Comparative 6.4 3.9 × 10⁶ <10² Example 23.2 3.8 × 10⁶ <10² 1.6 6.3 × 10⁶ <10² 0.8 5.2 × 10⁶ 6.0 × 10²Comparative 3.2 3.0 × 10⁶ <10² Example 4 1.6 3.8 × 10⁶ <10² 0.8 4.8 ×10⁶ 2.0 × 10² 0.4 5.0 × 10⁶ 1.7 × 10³ No treatment — 6.0 × 10⁶ 6.0 × 10⁶

TABLE 5 No heating Conc. Heating (Immediately after (ppm) (50° C., 4weeks) preparation) Example 6 2.0 <10² <10² 1.0 <10² <10² 0.5 <10² <10²0.25 4.0 × 10⁶ 9.5 × 10⁵ Example 7 2.0 <10² <10² 1.0 <10² <10² 0.5 <10²<10² 0.25 5.2 × 10⁶ 1.0 × 10⁶ Example 8 2.0 <10² <10² 1.0 <10² <10² 0.5<10² <10² 0.25 3.8 × 10⁶ 5.8 × 10⁵ Example 10 2.0 <10² <10² 1.0 <10²<10² 0.5 <10² <10² 0.25 7.6 × 10⁵ 4.2 × 10⁵ Example 11 2.0 <10² <10² 1.0<10² <10² 0.5 <10² <10² 0.25 4.2 × 10⁶ 5.0 × 10⁶ Example 12 2.0 <10²<10² 1.0 <10² <10² 0.5 <10² <10² 0.25 4.7 × 10⁶ 5.5 × 10⁶ Comparative4.0 4.5 × 10⁶ <10² Example 1 2.0 4.9 × 10⁶ <10² 1.0 5.0 × 10⁶ <10² 0.55.8 × 10⁶ 1.0 × 10³ Comparative 4.0 3.0 × 10⁶ <10² Example 2 2.0 3.8 ×10⁶ <10² 1.0 5.3 × 10⁶ <10² 0.5 5.5 × 10⁶ 3.0 × 10² Comparative 4.0 3.3× 10⁶ <10² Example 5 2.0 3.8 × 10⁶ <10² 1.0 4.8 × 10⁶ <10² 0.5 5.2 × 10⁶1.2 × 10³ No treatment — 5.8 × 10⁶ 5.8 × 10⁶

The results of Tables 4 and 5 show that for the Examples, almost equalmicrobicidal effects were displayed by those immediately afterpreparation and those that were allowed to stand for 4 weeks. Incontrast, the Comparative Examples were notably deactivated by heatingtreatment at 50° C. for 4 weeks. Specifically, it was found that theExamples are microbicidal liquid deodorants having excellent stabilityof active ingredients.

TEST EXAMPLE 3 Test of Fast-Acting Microbicidal Efficacy

Escherichia genus microbes, which were subjected to cell washing, werediluted with phosphate/citrate buffer solution (pH 8) to a concentrationof approximately 10⁶ CFU/ml, and 1 L each of the prepared solution waspoured into glass beakers. Example 1 or 8, and the powdered substance ofCompound A1 were each added thereto so as to bring to a prescribedconcentration (indicated based on active ingredient), respectively, andthe mixtures were stirred for 90 minutes. A portion of each mixture wastaken at 5, 10, 30, and 90 minutes and was diluted with sterilizedwater. Then, the diluted mixture was inoculated onto a nutrient plateagar medium and cultured in an incubator at 30° C. for 3 days. Then,viable cells therein were counted. The results are shown in Tables 6 and7 in the unit of CFU/ml. Tables 6 and 7 indicate the results obtained byconducting the tests over two separate occasions under the aboveconditions.

TABLE 6 Conc. Contact time (min.) (ppm) 5 10 30 90 Example 1 2.0 <10²<10² <10² <10² 1.5 <10² <10² <10² <10² 1.0 <10² <10² <10² <10² 0.5 <10²<10² <10² <10² 0.25 3.0 × 10⁶ 3.1 × 10⁶ 4.3 × 10⁶ 2.7 × 10⁵ Powder of2.0 1.0 × 10⁵ 2.0 × 10⁴ <10² <10² Compound A1 1.5 3.3 × 10⁶ 5.0 × 10⁴2.0 × 10² <10² 1.0 2.9 × 10⁶ 2.7 × 10⁵ 4.0 × 10³ <10² 0.5 3.0 × 10⁶ 7.7× 10⁵ 8.0 × 10⁴ <10² 0.25 3.0 × 10⁶ 3.1 × 10⁶ 4.5 × 10⁵ 3.7 × 10⁵ Notreatment — 4.0 × 10⁶ 3.7 × 10⁶ 5.0 × 10⁶ 1.1 × 10⁶

TABLE 7 Conc. Contact time (min) (ppm) 5 10 30 90 Example 8 2.0 <10²<10² <10² <10² 1.5 <10² <10² <10² <10² 1.0 <10² <10² <10² <10² 0.5 <10²<10² <10² <10² 0.25 5.8 × 10⁶ 5.6 × 10⁶ 3.0 × 10⁶ 2.0 × 10⁵ Powder of2.0 3.2 × 10⁵ 1.2 × 10⁴ <10² <10² compound A1 1.5 4.3 × 10⁶ 3.0 × 10⁴<10² <10² 1.0 4.8 × 10⁶ 2.9 × 10⁵ 8.8 × 10³ <10² 0.5 5.0 × 10⁶ 6.7 × 10⁵8.0 × 10⁴ <10² 0.25 5.6 × 10⁶ 5.1 × 10⁶ 3.7 × 10⁵ 2.7 × 10⁵ No treatment— 6.0 × 10⁶ 5.8 × 10⁶ 5.1 × 10⁶ 5.1 × 10⁶

The results of Tables 6 and 7 show that, compared with the solidcompound, the Examples had enhanced solubility into the target objectfor killing of microbes, and clarify that the Examples exhibit excellentmicrobicidal effects within a very short period. This property isrequired for disinfection or slime control of water for papermanufacturing processes, cooling water and washing water for variousindustrial uses, and the like, which require quick microbicidalactivity. These results show that the Examples are microbicidal liquiddeodorants suitable for disinfection or slime control of water for papermanufacturing processes and the like, which require fast-actingmicrobicidal activity.

TEST EXAMPLE 4 Test of Sustainability of Deodorant Effect Against ActiveSludge

Active sludge (dehydrated cake, water content 70%) obtained from asewage treatment plant was used for tests on the deodorant effect. Theobtained active sludge was suspended with distilled water to form a 40%suspension. Example 9, Comparative Example 2, or powdered Compound A2was then added to the suspension in a prescribed amount (indicated basedon active ingredient) and stirred. 200 g of each suspension containingExample 9, Comparative Example 2, or powdered Compound A2 wastransferred to a 1-liter Erlenmeyer flask, and the flask was sealed witha rubber stopper provided with 2 glass pipes each having a rubber tubeand a pinchcock. The volumes of ammonia, hydrogen sulfide, and methylmercaptan which were generated in a gas phase part of the 1-literErlenmeyer flask were measured after 1 hour and after 7 days. Themeasurement of each gas component was conducted by inserting a gasdetector tube into one of the rubber tubes with both pinchcocks open.Used herein were a gas detector 3L (GASTEC CORPORATION) for ammonia, agas detector 3L (GASTEC CORPORATION) for hydrogen sulfide, and a gasdetector 71 (GASTEC CORPORATION) for methyl mercaptan. The results areshown in Table 8. The symbol “ND” in the table indicates that a detectedvalue was equal to or lower than the detection limit of the detectortube.

TABLE 8 Volume of Volume of Volume of Hydrogen Methyl Ammonia sulfidemercaptan (ppm) (ppm) (ppm) 1 2 1 2 1 2 Conc. hour hours hour hours hourhours (ppm) later later later later later later Example 9 80 ND ND ND NDND ND 40 ND ND ND ND ND ND 20 1 ND ND ND ND ND 10 10 10 ND ND 0.5 NDComparative 80 ND 5.0 ND ND ND 0.5 Example 2 40 ND 20 ND 5.0 ND 5.0 205.0 40 ND 5.0 ND 10 10 20 40 2.5 5.0 5.0 10 Powder of 80 ND 20 ND 5.0 ND5.0 compound A2 40 10 40 2.5 5.0 0.5 10 20 40 40 5.0 5.0 10 10 10 40 405.0 5.0 10 10 No treatment — 40 40 5.0 5.0 10 10

The result of Table 8 shows that the Example exhibited an excellentdeodorant effect within a short period, compared with the solidcompound. This result indicates that the Example is a microbicidalliquid deodorant exhibiting an excellent deodorant effect within a shortperiod. Further, even under a condition of weak stirring andinsufficient mixing, because the Example was sufficiently dissolved andpermeated into the target object, it exhibited a rapid deodorant effectwith a smaller amount thereof.

1. A liquid microbicide comprising: one or more halogenated dialkylhydantoin represented by formula (1):

wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent lowalkyl groups, and a solvent comprising one or more thiophene derivative;wherein one or more thiophene derivative is selected from the groupconsisting of tetrahydrothiophene 1,1-dioxide,3-methyltetrahydrothiophene 1,1-dioxide, 2,5-dihydrothiophene1,1-dioxide, and mixtures thereof.
 2. The liquid microbicide accordingto claim 1, wherein one or more halogenated dialkyl hydantoin isselected from the group consisting of 1,3-dibromo-5,5-dimethylhydantoin,1-bromo-3-chloro-5,5-dimethylhydantoin,3-bromo-1-chloro-5,5-dimethylhydantoin,bromochloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin,1,3-dichloro-5-ethyl-5-methylhydantoin, and mixtures thereof.
 3. Theliquid microbicide according to claim 1, comprising one or morehalogenated dialkyl hydantoin and tetrahydrothiophene 1,1-dioxide. 4.The liquid microbicide according to claim 1, further comprising one ormore adjuvant; wherein one or more adjuvant is selected from the groupconsisting of hydantoin, 5,5-dimethylhydantoin, succinimide,phthalimide, and mixtures thereof.
 5. The liquid microbicide accordingto claim 1, further comprising a known microbicide component.
 6. Theliquid microbicide according to claim 1, wherein one or more thiophenederivative is present in an amount of 100 or more parts by mass based on100 parts by mass of halogenated dialkyl hydantoin.
 7. The liquidmicrobicide according to claim 1, wherein one or more thiophenederivative is present in an amount of 200 to 900 parts by mass, based on100 parts by mass of halogenated dialkyl hydantoin.
 8. A method forkilling microbes, which comprises: treating a target system or a targetobject for microbicidal treatment with an effective amount of anadmixture comprising one or more halogenated dialkyl hydantoinrepresented by formula (1):

wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent lowalkyl groups, and/or one or more halogenated succinimide represented byformula (2):

wherein Y represents a halogen atom; and a solvent comprising one ormore thiophene derivative; wherein one or more thiophene derivative isselected from the group consisting of tetrahydrothiophene 1,1-dioxide,3-methyltetrahydrothiophene 1,1-dioxide, 2,5-dihydrothiophene1,1-dioxide and mixtures thereof.
 9. A liquid deodorant comprising: oneor more halogenated dialkyl hydantoin represented by formula (1):

wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent lowalkyl groups, and a solvent comprising one or more thiophene derivative;wherein one or more thiophene derivative is selected from the groupconsisting of tetrahydrothiophene 1,1-dioxide,3-methyltetrahydrothiophene 1,1-dioxide, 2,5-dihydrothiophene1,1-dioxide; and mixtures thereof.
 10. The liquid deodorant according toclaim 9, wherein the halogenated dialkyl hydantoin is selected from thegroup consisting of 1,3-dibromo-5,5-dimethylhydantoin,1-bromo-3-chloro-5,5-dimethylhydantoin,3-bromo-1-chloro-5,5-dimethylhydantoin,bromochloro-5,5-dimethylhydantoin, 1,3-dichloro-5,5-dimethylhydantoin,1,3-dichloro-5-ethyl-5-methylhydantoin, and mixtures thereof.
 11. Theliquid deodorant according to claim 9, comprising one or morehalogenated dialkyl hydantoin and tetrahydrothiophene 1,1-dioxide. 12.The liquid deodorant according to claim 9, further comprising one ormore adjuvant; wherein one or more adjuvant is selected from the groupconsisting of hydantoin, 5,5-dimethylhydantoin, succinimide,phthalimide, and mixtures thereof.
 13. The liquid deodorant according toclaim 9, further comprising a known microbicide component.
 14. Theliquid deodorant according to claim 9, wherein one or more thiophenederivative is present in an amount of 100 or more parts by mass based on100 parts by mass of halogenated dialkyl hydantoin.
 15. The liquiddeodorant according to claim 9, wherein one or more thiophene derivativeis present in an amount of 200 to 900 parts by mass, based on 100 partsby mass of halogenated dialkyl hydantoin.
 16. A deodorizing method,which comprises: treating a target system or a target object fordeodorization with an effective amount of an admixture comprising one ormore halogenated dialkyl hydantoin represented by formula (1):

wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent lowalkyl groups, and/or one or more halogenated succinimide represented byformula (2):

wherein Y represents a halogen atom; and a solvent comprising one ormore thiophene derivative; wherein one or more thiophene derivative isselected from the group consisting of tetrahydrothiophene 1,1-dioxide,3-methyltetrahydrothiophene 1,1-dioxide, 2,5-dihydrothiophene1,1-dioxide and mixtures thereof.
 17. A method for stabilizing ahalogenated dialkyl hydantoin and/or halogenated succinimide, whichcomprises: dissolving at least one substance selected from the groupconsisting of one or more halogenated dialkyl hydantoin represented byformula (1):

wherein X₁ and X₂ represent halogen atoms and R₁ and R₂ represent lowalkyl groups, and/or one or more halogenated succinimide represented byformula (2):

wherein Y represents a halogen atom; in a solvent comprising one or morethiophene derivative; wherein one or more thiophene derivative isselected from the group consisting of tetrahydrothiophene 1,1-dioxide,3-methyltetrahydrothiophene 1,1-dioxide, 2,5-dihydrothiophene1,1-dioxide and mixtures thereof.
 18. A method for stabilizing ahalogenated dialkyl hydantoin and/or halogenated succinimide accordingto claim 17, wherein at least one substance is selected from the groupconsisting of hydantoin, 5,5-dimethylhydantoin, succinimide, andphthalimide.